High refractive index self-healing pc, preparation method and application thereof

Abstract

The application provides a high-refractive self-healing PC and a preparation method and application thereof. The self-healing PC is prepared by introducing a self-healing monomer and a refractive functional monomer. The high-refractive self-healing PC prepared by the application further improves the refractive index of the PC, and meanwhile, the defect that the PC is easily damaged by scratching is improved, and the self-healing of the PC gap can be realized at 40 DEG C or above.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a high-refractive self-healing PC and a preparation method and application thereof. BACKGROUND

[0002] Polycarbonate (PC) is widely used in the fields of electronics, automobiles, construction and optics as an engineering plastic. PC has good tensile mechanical properties and excellent optical properties. In the field of lenses, PC has a low cost, but is limited by its low refractive index and is mainly used in the field of medical protective glasses.

[0003] In addition, PC has weak scratch resistance when used as a lens. The surface of PC parts is often scratched, resulting in poor use effect. The scratch can be repaired by coating the PC substrate, but this will make the production process more complicated and increase the processing cost of PC lenses. In addition, the coating may affect the refractive index, light transmittance and fall off after a long time.

[0004] Therefore, there is still a need to develop a new PC with high refractive index, which can easily restore the morphology of scratches while further improving the refractive index. SUMMARY

[0005] The purpose of the present application is to provide a PC with high refractive index and self-healing. By adding NASC third monomer and p-phenylene diisothiocyanate during the synthesis of PC, the molecular structure of PC is modified, which greatly improves the high refractive index of PC and restores the surface morphology of the product to its original state through heat treatment when the surface of the product is scratched.

[0006] Another purpose of the present application is to provide a preparation method and application of the PC with high refractive index and self-healing.

[0007] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0008] A PC with high refractive index and self-healing has the following structure:

[0009]

[0010] wherein R1 is NASC, the molecular formula is CO(NH)2COCHCH2, and R2 is a monophenol.

[0011] In a preferred embodiment, the refractive index of the PC with high refractive index and self-healing of the present application can be increased to 1.8 or more, preferably 2 or more, such as 2, 2.1, 2.2, 2.3, 2.4, etc., and the self-repairing rate can be increased to 90% or more, preferably 95% or more, and more preferably 99% or more.

[0012] In another aspect, the aforementioned method for preparing a high refractive index self-healing PC comprises the following steps:

[0013] 1) mixing bisphenol A and alkali liquor to obtain a homogeneous aqueous solution a;

[0014] 2) adding an oil-soluble solvent to the homogeneous aqueous solution a to obtain an oil-water mixture b;

[0015] 3) continuously passing phosgene and alkali liquor into the oil-water mixture b to react;

[0016] 4) adding p-phenylene diisothiocyanate, NASC, p-tert-butyl phenol and a catalyst, and continuously passing alkali liquor to continue the reaction for a period of time to obtain a PC reaction liquid;

[0017] 5) taking the oil phase of the PC reaction liquid, removing the oil-soluble solvent after acid washing and water washing to obtain PC solid.

[0018] In some specific embodiments, in step 1), the mass concentration of bisphenol A in the homogeneous aqueous solution a is 10-20 wt%, for example 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, etc.

[0019] The alkali liquor is an aqueous solution of NaOH and / or KOH, and the mass concentration of the alkali liquor in the homogeneous aqueous solution a is 4-7 wt%, for example 4 wt%, 5 wt%, 6 wt%, 7 wt%, etc.

[0020] In some specific embodiments, in step 2), the oil-soluble solvent can be one or more of chloroform, tetrachloroethane, dichloromethane, chlorobenzene, tetrahydrofuran, dioxane, pyridine, and the mass ratio of the homogeneous aqueous solution a to the oil-soluble solvent is 0.5-1.5, for example 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc., preferably 0.9-1.1.

[0021] In some specific embodiments, in step 3), the molar ratio of phosgene to bisphenol A is 1-2, for example 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc.

[0022] In step 3), the alkali liquor is an aqueous solution of NaOH and / or KOH with a mass concentration of 5wt%-50wt%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., and is introduced at a flow rate of 1-10 g / min during the reaction, such as 1 g / min, 2 g / min, 3 g / min, 4 g / min, 5 g / min, 6 g / min, 7 g / min, 8 g / min, 9 g / min, 10 g / min, etc.

[0023] In step 3), the reaction temperature is 15°C-36°C, such as 16°C, 18°C, 19°C, 20°C, 25°C, 28°C, 30°C, 33°C, 35°C, 36°C, etc., and the reaction time is 5-10 min, such as 6 min, 7 min, 8 min, 9 min, 10 min, etc.

[0024] In some specific embodiments, in step 4), preferably, the catalyst is triethylamine or a quaternary ammonium salt, such as N, N, N, N-trimethyl benzyl ammonium chloride, N, N, N, N-dimethyl ethyl octadecyl ammonium sulfate, and more preferably triethylamine is used, and the content of the catalyst in the reaction solution in step (4) is 50-500 ppm, such as 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, etc.

[0025] In step 4), the molar ratio of p-phenylene diisothiocyanate to bisphenol A is 0.01-0.08, such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, etc.; the molar ratio of NASC to bisphenol A is 0.01-0.05, such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, etc.; and the molar ratio of p-t-butylphenol to bisphenol A is 0-0.08, such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, etc.

[0026] In step 4), the alkaline solution is an aqueous solution of NaOH and / or KOH, preferably an aqueous solution of NaOH, more preferably the same as the alkaline solution in step 3); the mass concentration of the alkaline solution is 5wt%-50wt%, for example 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., preferably 32%; the alkaline solution is introduced at a flow rate of 0.1-1g / min during the reaction, for example at a flow rate of 1g / min, 2g / min, 3g / min, 4g / min, 5g / min, 6g / min, 7g / min, 8g / min, 9g / min, 10g / min, etc.

[0027] In step 4), preferably, the reaction temperature is controlled in the range of 25°C-36°C, for example 25°C, 28°C, 30°C, 33°C, 35°C, 36°C, etc.; preferably, the reaction time is 5-40min, for example 6min, 7min, 8min, 9min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, etc.

[0028] In some specific embodiments, in step 5), the oil phase of the PC reaction solution can be separated by conventional techniques in the art, for example after standing and layering, or can be separated by extraction, etc., without particular limitation. In the present application, the acid used for acid washing can be a strong acid such as hydrochloric acid, sulfuric acid, nitric acid, etc., preferably hydrochloric acid, and the mass concentration of the acid can be 0.5wt%-10wt%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc., preferably 1wt%. The number of times of acid washing and water washing is not particularly limited, for example 2-5 times, and after water washing, the oil-soluble solvent is removed, for example by flash evaporation, to obtain PC solids, and the content of the catalyst in the solid product is less than 0.3ppm, the content of chloride ions is less than 10ppm, and the content of the oil-soluble solvent is less than 100ppm.

[0029] In the present application, by adding NASC as a third monomer during the synthesis of PC, the molecular structure of PC is modified, wherein NASC is a substance with high hydrogen bond density, and after being introduced into PC, when the surface of the product is scratched, the surface morphology of the product can be restored by heat treatment, and the required temperature is low. More importantly, in order to further enhance the high refractive ability of PC, p-phenylene diisothiocyanate is introduced during the synthesis of PC, which can greatly improve the high refractive ability of PC. After the refractive ability is improved, the PC lens or lens can be made lighter and thinner under the same refractive effect, greatly expanding the application field of PC in lenses, and greatly improving the application experience.

[0030] In still another aspect of the present application, the high-refractive self-healing PC or the high-refractive self-healing PC prepared by the aforementioned preparation method is applied in the field of optical devices, lasers, LEDs, etc.

[0031] Compared with the prior art, the present application has the following advantages:

[0032] 1) The high-refractive self-healing PC material of the present application greatly improves the refractive ability of PC by introducing p-phenylene diisothiocyanate into the PC molecular chain.

[0033] 2) The high-refractive self-healing PC material of the present application can restore the surface morphology of the scratched product to the original state through low-temperature heat treatment at 40-60℃ after the surface of the PC product is scratched due to the addition of NASC photosensitive monomer.

[0034] 3) Compared with the prior art, the present application first prepares a new type of high-refractive self-healing PC, optimizes the molecular structure of PC, and has stronger stability and simpler processing compared with the current commonly used film coating technology. DETAILED DESCRIPTION

[0035] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0036] The main raw materials involved in the following examples are as follows:

[0037] NASC refers to the patent "A Supramolecular Copolymer Hydrogel and a Preparation Method Thereof" (0020 paragraph of CN112521550A).

[0038] The remaining materials are not particularly specified and can be purchased on the market.

[0039] The test methods involved in the following examples are as follows:

[0040] The refractive index is tested by Abbe refractometer (model: WYA-2S) according to standard QB / T 2506-2017, and the test wavelength is 587.56nm.

[0041] Repair rate test: prepare tensile sample according to GB / T 1040-1992, use a blade to draw a 1mm deep scratch in the middle of the narrow neck, use WDW-05 type electronic mechanics tensile machine (China Times Group Co., Ltd.) to test the tensile test of the sample of the control group at room temperature, then use the same drawing treatment to the tensile sample, and then use ultraviolet light to irradiate for 10 min, and then perform the same tensile test, record the tensile strength of different samples, test three times and take the average value. The self-repairing efficiency (HE) is an important parameter to measure the self-repairing performance of the material, and the specific calculation formula is as follows: Wherein, S H represents the tensile strength of the PC sample of the experimental group, and S0 represents the tensile strength of the PC sample of the control group.

[0042] Example 1

[0043] A 2L jacketed reactor was added with 540g of deionized water under the protection of nitrogen, then 31g of solid NaOH was added, and the stirring was started. After adjusting the temperature to 32℃, 80g of bisphenol A solid was added, and the stirring was continued for 30min until the bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0044] 650g of dichloromethane was added to the reactor, and the stirring speed was adjusted to 300r / min to mix the water phase and the oil phase uniformly;

[0045] 9.4L of phosgene gas was introduced into the reactor at a rate of 0.94L / min, and 32wt% NaOH lye was added to the reactor at a rate of 1.9g / min, and the reaction temperature was controlled at 35℃ during the process;

[0046] 4g of p-phenylene diisothiocyanate, 3g of NASC, 7.5g of 10wt% PTBP solution, 78ppm of triethylamine were added to the reactor, and 32wt% NaOH lye was added to the reactor at a rate of 0.28g / min, and the stirring was continued for 30min, then stopped, and the reaction temperature was controlled at 28℃ during the process;

[0047] After the water and oil phases were separated, the oil phase was first washed with 1.5% HC1 solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then the MC was removed and dried to obtain PC solid;

[0048] The plate vulcanizing machine was used to press it into a 3mm plate at 300℃, and the heat preservation time was 40min. The refractive index was 2.3, and the repair rate was 99%.

[0049] Example 2

[0050] Into a 2L jacketed reactor under nitrogen protection, 540g of deionized water was added, then 31g of solid NaOH was added, and stirring was started to dissolve. After adjusting the temperature to 32°C, 80g of solid bisphenol A was added, and stirring was continued for 30min until bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0051] 650g of chlorobenzene was added to the reactor, and the stirring speed was adjusted to 300r / min to mix the water phase and the oil phase uniformly;

[0052] At a rate of 0.94L / min, 9.4L of gaseous phosgene was introduced into the reactor, and at a rate of 1.9g / min, 32wt% NaOH lye was added to the reactor, and the reaction temperature was controlled at 35°C during the process;

[0053] 2.5g of p-phenylene diisothiocyanate, 1g of NASC, 2.3g of 10wt% PTBP solution, and 78ppm of triethylamine were added to the reactor, and at a rate of 0.28g / min, 32wt% NaOH lye was added to the reactor, and stirring was continued for 30min before stopping, and the reaction temperature was controlled at 28°C during the process;

[0054] After the water and oil phases were separated, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then MC was removed and dried to obtain PC solid;

[0055] It was pressed into a 3mm plate using a flat vulcanizing machine at 300°C for 40min. The refractive index was 2, and the repair rate was 98%.

[0056]

Example 3

[0057] Into a 2L jacketed reactor under nitrogen protection, 540g of deionized water was added, then 31g of solid NaOH was added, and stirring was started to dissolve. After adjusting the temperature to 32°C, 80g of solid bisphenol A was added, and stirring was continued for 30min until bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0058] 650g of chlorobenzene was added to the reactor, and the stirring speed was adjusted to 300r / min to mix the water phase and the oil phase uniformly;

[0059] At a rate of 0.94L / min, 9.4L of gaseous phosgene was introduced into the reactor, and at a rate of 1.9g / min, 32wt% NaOH lye was added to the reactor, and the reaction temperature was controlled at 35°C during the process;

[0060] Into a reaction kettle, 1 g of p-phenylene diisothiocyanate, 0.6 g of NASC, 4.7 g of PTBP solution with a concentration of 10 wt%, 78 ppm of triethylamine were added, and 32 wt% NaOH lye was added to the reaction kettle at a rate of 0.28 g / min, and the reaction was continuously stirred for 30 min and then stopped, during which the reaction temperature was controlled at 28°C;

[0061] After the water and oil phases were separated, the oil phase was first washed with 1.5% HC1 solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then the MC was removed and dried to obtain PC solid;

[0062] It was pressed into a 3 mm plate using a flat vulcanizing machine at 300°C, and the temperature was kept for 40 min. The refractive index was 1.9, and the repair rate was 96%.

[0063]

Example 4

[0064] Into a 2 L jacketed reaction kettle, 540 g of deionized water was added under the protection of nitrogen, and then 31 g of solid NaOH was added, and stirring was started to dissolve. After adjusting the temperature to 32°C, 80 g of bisphenol A solid was added, and stirring was continued for 30 min until the bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0065] Into the reaction kettle, 650 g of tetrahydrofuran was added, and the stirring speed was adjusted to 300 r / min to mix the water and oil phases uniformly;

[0066] Into the reaction kettle, 9.4 L of gaseous phosgene was introduced at a rate of 0.94 L / min, and 32 wt% NaOH lye was added to the reaction kettle at a rate of 1.9 g / min, and the reaction temperature was controlled at 35°C during the reaction;

[0067] Into the reaction kettle, 0.5 g of p-phenylene diisothiocyanate, 2 g of NASC, 4.7 g of PTBP solution with a concentration of 10 wt%, 78 ppm of triethylamine were added, and 32 wt% NaOH lye was added to the reaction kettle at a rate of 0.28 g / min, and the reaction was continuously stirred for 30 min and then stopped, during which the reaction temperature was controlled at 28°C;

[0068] After the water and oil phases were separated, the oil phase was first washed with 1.5% HC1 solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then the MC was removed and dried to obtain PC solid;

[0069] It was pressed into a 3 mm plate using a flat vulcanizing machine at 300°C, and the temperature was kept for 40 min. The refractive index was 1.8, and the repair rate was 99%.

[0070]

Example 4

[0071] Into a 2L jacketed reactor, 540g of deionized water was added under nitrogen protection, then 31g of solid NaOH was added, and stirring was started to dissolve. After adjusting the temperature to 32℃, 80g of solid bisphenol A was added, and stirring was continued for 30min until bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0072] 650g of dichloromethane was added to the reactor, and the stirring speed was adjusted to 300r / min to mix the water phase and oil phase uniformly;

[0073] 9.4L of gaseous phosgene was introduced into the reactor at a rate of 0.94L / min, and 32wt% NaOH lye was added to the reactor at a rate of 1.9g / min, while the reaction temperature was controlled at 35℃;

[0074] 4g of p-phenylene diisothiocyanate, 7.5g of 10wt% PTBP solution, and 78ppm of triethylamine were added to the reactor, and 32wt% NaOH lye was added to the reactor at a rate of 0.28g / min, and stirring was continued for 30min before stopping, while the reaction temperature was controlled at 28℃;

[0075] After separating the water and oil phases, the oil phase was first washed with 1.5% HCl solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then MC was removed and dried to obtain PC solid;

[0076] It was pressed into a 3mm plate using a flat vulcanizing machine at 300℃ for 40min. The refractive index was 2.1, and the repair rate was 0.

[0077]

Comparative Example 2

[0078] Into a 2L jacketed reactor, 540g of deionized water was added under nitrogen protection, then 31g of solid NaOH was added, and stirring was started to dissolve. After adjusting the temperature to 32℃, 80g of solid bisphenol A was added, and stirring was continued for 30min until bisphenol A was completely dissolved to obtain a homogeneous aqueous solution;

[0079] 650g of dichloromethane was added to the reactor, and the stirring speed was adjusted to 300r / min to mix the water phase and oil phase uniformly;

[0080] 9.4L of gaseous phosgene was introduced into the reactor at a rate of 0.94L / min, and 32wt% NaOH lye was added to the reactor at a rate of 1.9g / min, while the reaction temperature was controlled at 35℃;

[0081] Into a reaction kettle, 3g of NASC, 7.5g of PTBP solution with a concentration of 10wt%, 78ppm of triethylamine were added, and 32wt% of NaOH lye was added into the reaction kettle at a rate of 0.28g / min, and the reaction was continuously stirred for 30min, and then stopped, during which the reaction temperature was controlled at 28℃;

[0082] After the water and oil phases were separated, the oil phase was first washed with 1.5% of HCl solution, and then the oil phase was washed with deionized water until the water after washing was neutral. Then the MC was removed and dried to obtain PC solid;

[0083] It was pressed into a 3mm plate using a flat vulcanizing machine at 300℃, and the temperature was kept for 40min. The refractive index was 1.6, and the repair rate was 90%.

[0084] The applicant declares that the two-component polyurethane heat-conducting structural adhesive and the preparation method thereof are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement on the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. all fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a high refractive index self-healing PC, characterized in that, Includes the following steps: 1) Bisphenol A and alkaline solution are mixed to obtain a homogeneous aqueous solution a; 2) Adding an oil-soluble solvent to a homogeneous aqueous solution a yields an oil-water mixture b; 3) Phosgene and alkaline solution are continuously introduced into the oil-water mixture b to carry out the reaction; 4) Add terephthalic diisothiocyanate, NASC, p-tert-butylphenol and catalyst, and continuously pass alkali solution through to continue the reaction for a period of time to obtain PC reaction solution; 5) Take the oil phase of the PC reaction solution, and remove the oil-soluble solvent by acid washing and water washing to obtain solid PC.

2. The preparation method according to claim 1, characterized in that, In step 1), the mass concentration of bisphenol A in the homogeneous aqueous solution a is 10-20 wt%; and / or The alkaline solution is an aqueous solution of NaOH and / or KOH, with a mass concentration of 4-7 wt% in the homogeneous aqueous solution a.

3. The preparation method according to claim 1 or 2, characterized in that, In step 2), the oil-soluble solvent is selected from one or more of chloroform, tetrachloroethane, dichloromethane, chlorobenzene, tetrahydrofuran, dioxane, and pyridine.

4. The preparation method according to claim 3, characterized in that, The mass ratio of the homogeneous aqueous solution a to the oil-soluble solvent is 0.5-1.

5.

5. The preparation method according to claim 1, characterized in that, In step 3), the molar ratio of phosgene to bisphenol A is 1-2; and / or The alkaline solution is an aqueous solution of NaOH and / or KOH with a mass concentration of 5wt%-50wt%, and is introduced at a flow rate of 1-10g / min during the reaction.

6. The preparation method according to claim 5, characterized in that, The reaction time is 5-10 minutes.

7. The preparation method according to claim 1, characterized in that, In step 4), the molar ratio of terephthalic diisothiocyanate to bisphenol A is 0.01 to 0.08; the molar ratio of NASC to bisphenol A is 0.01 to 0.05; and the molar ratio of p-tert-butylphenol to bisphenol A is 0.02 to 0.

08.

8. The preparation method according to claim 7, characterized in that, In step 4), the catalyst is triethylamine and / or a quaternary ammonium salt.

9. The preparation method according to claim 8, characterized in that, The amount of catalyst added is 50-500 ppm of the mass of the reaction solution in step 3).

10. The preparation method according to claim 1, characterized in that, In step 4), the alkaline solution is an aqueous solution of NaOH and / or KOH with a mass concentration of 5wt%-50wt%, and is introduced at a flow rate of 1-10g / min during the reaction.

11. The preparation method according to claim 10, characterized in that, In step 4), the reaction time is 5-40 minutes.

12. The high refractive index self-healing PC prepared by the preparation method according to any one of claims 1-11.

13. The high refractive index self-healing PC according to claim 12, characterized in that, The self-healing PC has a refractive index of 1.8 or higher and a self-repair rate of 90% or higher.

14. The application of the high refractive index self-healing PC prepared by the preparation method according to any one of claims 1-11 or the high refractive index self-healing PC according to claim 12 or 13 in the fields of optical devices, lasers, and LEDs.

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